A method for treating lignin and for producing a binder composition

ABSTRACT

The invention relates to a method for treating lignin, wherein the method comprises the following steps: a) dissolving lignin into an aqueous composition, which contains a compound selected from the class of phenols, while keeping the temperature of the composition at 0-60° C.; and b) allowing the composition to react while keeping the temperature of the composition at 60-100° C. and the pH of the composition at a pH value of 6-14. The invention relates further to a method for producing a binder composition and to dissolve lignin into an aqueous composition different applications thereof.

FIELD OF THE INVENTION

The invention relates to a method for treating lignin and to the usethereof for producing a binder composition as well as to differentapplications thereof.

BACKGROUND OF THE INVENTION

Lignin is a natural polymer, which can be extracted from e.g. wood. Aslignin is a natural biopolymer its use as a component in glues insteadof synthetic materials has been investigated in order to come up with amore environmentally friendly adhesive composition. Especially, theability to replace synthetic phenol in phenolic resins, such as phenolformaldehyde resin, has been the object of prior art. Lignin can be usedfor the purpose of decreasing the amount of synthetic phenol in a resincomposition. Lignin has previously been used for replacing phenol duringthe production of lignin-phenol-formaldehyde resin.

The currently known lignin based resins are not, however, suitable forall the applications where traditional phenolic resins are being used.For example, the currently known lignin based resins are not suitablefor high-pressure laminates. High-pressure laminates (HPL), which arealso known as plastic laminates, can be produced by fusing togetherunder the influence of heat and pressure, multiple layers of paper,fabrics, or other core materials by using thermosetting resins asbinders. The inventors have recognized a need for a method, which wouldresult in a higher phenol replacement in the resin and thus in a moreenvironmentally friendly binder composition having suitable propertiesfor use in different applications such as high-pressure laminates.

PURPOSE OF THE INVENTION

The purpose of the invention is to provide a new type of method fortreating lignin and to provide a method for producing a bindercomposition for different applications. The purpose of the invention isto provide a new binder composition and adhesive composition as well asthe uses thereof.

SUMMARY

The method for treating lignin according to the present invention ischaracterized by what is presented in claim 1.

The method for producing a binder composition according to the presentinvention is characterized by what is presented in claim 10.

The binder composition obtainable by the method according to the presentinvention is characterized by what is presented in claim 20.

The adhesive composition according to the present invention ischaracterized by what is presented in claim 21.

The uses according to the present invention are characterized by what ispresented in claims 19, 22, 23 and 24.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying drawings, which are included to provide a furtherunderstanding of the invention and constitute a part of thisspecification, illustrate embodiments of the invention and together withthe description help to explain the principles of the invention. In thedrawings:

FIG. 1 is a flow chart illustration of a method for treating ligninaccording to one embodiment of the present invention; and

FIG. 2 is a flow chart illustration of a method for producing a bindercomposition according to one embodiment of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a method for treating lignin, whichmethod comprises the following steps:

a) dissolving lignin into an aqueous composition, which contains acompound selected from the class of phenols, while keeping thetemperature of the composition at 0-60° C.; and

b) allowing the composition to react while keeping the temperature ofthe composition at 60-100° C. and the pH of the composition at a pHvalue of 6-14.

The present invention further relates to a method for producing a bindercomposition, wherein the method comprises the following steps:

a) dissolving lignin into an aqueous composition, which contains acompound selected from the class of phenols, while keeping thetemperature of the composition at 0-60° C.;

b) allowing the composition to react while keeping the temperature ofthe composition at 60-100° C. and the pH of the composition at a pHvalue of 6-14; and

c) mixing the composition formed in step b) with a crosslinking agentand heating the composition at a temperature of 60-100° C. while keepingthe pH of the composition at a pH value of 6-14.

In one embodiment of the present invention lignin is dissolved into acomposition, which consists of water and at least one compound selectedfrom the class of phenols, in step a). In one embodiment of the presentinvention lignin is dissolved into an aqueous composition of a compoundselected from the class of phenols.

In one embodiment of the present invention the compound selected fromthe class of phenols is selected from a group consisting of phenol,cresol, resorcinol and combinations thereof. In one embodiment of thepresent invention the compound selected from the class of phenols isphenol.

In one embodiment of the present invention the alkali is added to thecomposition in step a). In one embodiment of the present inventionalkali is added to the composition in step b). In one embodiment of thepresent invention alkali is added to the composition in step a) and instep b).

In one embodiment of the present invention the alkali comprises ahydroxide of an alkali metal.

Step b) comprises allowing the composition to react, i.e. step b)comprises allowing reactions to take place in the composition. In oneembodiment of the present invention step b) comprises allowing thecomposition to react with alkali, wherein the alkali comprises ahydroxide of an alkali metal.

The inventors of the present invention surprisingly found out thatdissolving lignin into a composition of e.g. phenol and water, withoutallowing the lignin to actually react with the phenol due to thespecific temperature used, advantageously affects the step of producinga binder composition and enables the production of a binder compositionwith a low pH value if desired. Without limiting the invention to anyspecific theory of why the above advantage can be achieved, it is to beconsidered that when lignin is dissolved into a composition of e.g.phenol and water, no covalent bonds are formed, but the reactive sitesof both lignin and phenol are present in a sterically beneficialposition with regard to the further reactions taking place during theproduction of the binder composition. The inventors of the presentinvention found out that by the method of the present invention it waspossible to produce a lignin based binder composition that is suitablefor e.g. the production of high-pressure laminates.

In one embodiment of the present invention lignin is allowed to reactwith the compound selected from the class of phenols in step b) byadjusting the temperature and the pH to a suitable level.

In one embodiment of the present invention step b) is carried out foralkalating the lignin. The alkalation step results in the lignin beingactivated. Without limiting the invention to any specific theory aboutwhy alkalation of lignin results in a more activated or more reactivelignin being formed compared to non-alkalated lignin, it is to beconsidered that the alkalation opens the macromolecular structure oflignin whereby the steric hindrances that usually disable reactivegroups in lignin structures are removed. Alkalation may also add chargedgroups to the lignin macromolecule. In one embodiment of the presentinvention treating lignin with the method according to the presentinvention activates the lignin. The advantage of using alkalated lignine.g. for producing a binder composition is that the compatibility andreaction behavior is much better than in a normal case, wherenon-treated lignin has been used in the cooking or polymerizing stage ofproduction process.

The inventors surprisingly found out that when dissolving lignin intophenol, the phenol is sterically close to the reactive sites of thelignin. When these reactant components are allowed to react in step c)of the method according to the present invention with a crosslinkingagent, e.g. formaldehyde, the used crosslinking agent will react equallywith both components allowing the formation of a binder compositionhaving a high ratio of bio-based materials.

In this specification, unless otherwise stated, the expression “lignin”should be understood as lignin originating from any suitable ligninsource.

The lignin used can be essentially pure lignin. By the expression“essentially pure lignin” should be understood as at least 90% purelignin, preferably at least 95% pure lignin. In one embodiment of thepresent invention the essentially pure lignin comprises at most 10%,preferably at most 5%, of other components. Extractives andcarbohydrates such as hemicelluloses can be mentioned as examples ofsuch other components. In one embodiment of the present invention thelignin contains less than 10 weight-%, preferably less than 6 weight-%,and more preferably less than 4 weight-% of carbohydrates. The amount ofcarbohydrates present in lignin can be measured by high performanceanion exchange chromatography with pulsed amperometric detector(HPAE-PAD) in accordance with standard SCAN-CM 71.

In one embodiment of the present invention the ash percentage of ligninis less than 7.5 weight-%, preferably less than 5 weight-%, and morepreferably less than 3 weight-%. The ash content can be determined bycarbonifying and quickly burning a lignin sample so that alkali saltsare not melted before the organic matter has been burned (e.g. 20-200°C. for 30 minutes, after which temperature is adjusted to 200-600° C.for 1 h, and thereafter adjusting the temperature to 600-700° C. for 1hour), and finally the lignin sample is ignited at 700° C. for 1 h. Ashcontent of a lignin sample refers to the mass that remains of the sampleafter burning and ignition, and it is presented as per cent of thesample's dry content.

In one embodiment of the present invention the weight average molecularweight (Mw) of lignin is 1000-15000 g/mol, preferably 2000-10000 g/mol,and more preferably 3000-8000 g/mol. The molecular weight of the lignincan be determined by using a high-performance size-exclusionchromatography in the following manner: Two parallel measurements arecarried out. 0.1 M NaOH is used as an eluent. Calibration is done usingNa-polystyrene sulfonate standards having a molecular weight of1100-73900 g/mol. For quality control, standard quality kraft lignin andPSS molecular weight standard are used. The columns used are PSS MCXprecolumns, 1000 Å and 100 000 Å separation columns filled withsulfonated styrene-divinylbenzene copolymer matrix. Isocratic runprogram is used. The run time is 45 minutes. The injection volume is 50μl. The flux is 0.5 ml per minute. The temperature is 25° C. As a resultof the chromatography, number average molecular weight (Mn), weightaverage molecular weight (Mw), peak molecular weight (Mp) andpolydispersity index (PDI) values can be reported.

In one embodiment of the present invention the number average molecularweight (Mn) of lignin is 700-4000, preferably 800-3000, and morepreferably 1000-2500.

In one embodiment of the present invention the polydispersity of ligninis 1.0-7, preferably 1.2-6, and more preferably 1.4-4.5.

In one embodiment of the present invention the normalized radicalscavenger index (NRSI) of lignin is 0.01-20, preferably 0.05-10, andmore preferably 0.1-6. The antioxidant activity of extracts can beevaluated using DPPH-method in methanol extracts.

The basis of the radical scavenging method is described in Malterud etal. (Pharmacol. Toxicol. 1996, 78: 111-116). The method is based on theability of extracts and pure components to react with1,1,-diphenylpicryl-2-hydrazylradical (DPPH.)-molecules when DPPH losesits radical characteristic. The decline of radical form can be observedwith spectrophotometer as a change of solution color from violet toyellow (absorbance is measured at wavelength 515 nm). RSI (radicalscavenging index) is defined as the inverse of the concentration thatproduced 50% inhibition in DPPH absorbance at 515 nm. The results canthen be “normalized” (NRSI) by dividing the sample RSI by the RSI valuefor the butyl hydroxytoluene (BHT) control.

In one embodiment of the present invention the dry solids content oflignin is below 98%, preferably 40-80%, and more preferably 50-70%. Thedry solids content can be measured by drying a lignin sample of 1-5 g ata temperature of 60° C. or above in a vacuum oven for four hours.

In one embodiment of the present invention the lignin has an amount of0.1-6 mmol, preferably 0.3-3.5 mmol of aliphatic hydroxyl groups pergram of dry lignin.

In one embodiment of the present invention the lignin has an amount of0.1-5 mmol, preferably 1.5-4.5 mmol of phenolic hydroxyl groups per gramof dry lignin. Aliphatic and phenolic hydroxyl groups can be determinedby characterizing a lignin sample with 31P NMR spectroscopy afterphosphitylation and after which the aliphatic hydroxyl groups can bequantitatively determined. For 31P NMR analyses 40 mg of lignin can beweighted and dissolved in 300 μl of N,N-dimethylformamide. After totaldissolution 200 μl of pyridine, 400 μl (0.05M) of internal standardsolution (ISTD) of Endo-N-Hydroxy-5-norbornene-2,3-dicarboximide inpyridine/CDCl₃ and 100 μl of Cr(acac)₃ solution in pyridine/CDCl₃ isadded. Then 200 μl of phosphitylation reagent2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphopholane is added drop-wise.Finally 600 μl of CDCl₃ is added to the solution and clear brown toblack solution is achieved. Freshly prepared samples can then bemeasured with 31P NMR at room temperature. Bruker 500 MHz NMRspectrometer can be used for the measurement. 31P NMR measurement isbased on the method developed by Grannata and Argyropoulos (Grannata A.and Argyropoulos D. S.,2-Chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane, a reagent for theaccurate determination of the uncondensed and condensed phenolicmoieties in lignins. J. Agric. Food Chem, 1995, 43:1538-1544). Theresults are calculated as mmol/g lignin.

In one embodiment of the present invention the lignin is selected from agroup consisting of kraft lignin, steam explosion lignin, biorefinerylignin, supercritical separation lignin, hydrolysis lignin, flashprecipitated lignin, biomass originating lignin, lignin from alkalinepulping process, lignin from soda process, lignin from organosolspulping and combinations thereof. In one embodiment of the presentinvention the lignin is wood based lignin. The lignin can originate fromsoftwood, hardwood, annual plants or from a combination thereof.

Different lignin components may have different properties, e.g.molecular weight, molar mass, polydispersity, hemicellulose andextractive contents and compositions.

By “kraft lignin” is to be understood in this specification, unlessotherwise stated, lignin that originates from kraft black liquor. Blackliquor is an alkaline aqueous solution of lignin residues,hemicellulose, and inorganic chemicals used in a kraft pulping process.The black liquor from the pulping process comprises componentsoriginating from different softwood and hardwood species in variousproportions. Lignin can be separated from the black liquor by differenttechniques including e.g. precipitation and filtration. Lignin usuallybegins precipitating at pH values below 11-12. Different pH values canbe used in order to precipitate lignin fractions with differentproperties. These lignin fractions differ from each other by molecularweight distribution, e.g. Mw and Mn, polydispersity, hemicellulose andextractive contents. The molar mass of lignin precipitated at a higherpH value is higher than the molar mass of lignin precipitated at a lowerpH value. Further, the molecular weight distribution of lignin fractionprecipitated at a lower pH value is wider than of lignin fractionprecipitated at a higher pH value.

The precipitated lignin can be purified from inorganic impurities,hemicellulose and wood extractines using acidic washing steps. Furtherpurification can be achieved by filtration.

In one embodiment of the present invention the lignin is flashprecipitated lignin. The term “flash precipitated lignin” should beunderstood in this specification as lignin that has been precipitatedfrom black liquor in a continuous process by decreasing the pH of ablack liquor flow, under the influence of an over pressure of 200-1000kPa, down to the precipitation level of lignin using a carbon dioxidebased acidifying agent, preferably carbon dioxide, and by suddenlyreleasing the pressure for precipitating lignin. The method forproducing flash precipitated lignin is disclosed in patent applicationFI 20106073. The residence time in the above method is under 300 s. Theflash precipitated lignin particles, having a particle diameter of lessthan 2 μm, form agglomerates, which can be separated from black liquorusing e.g. filtration. The advantage of the flash precipitated lignin isits higher reactivity compared to normal kraft lignin. The flashprecipitated lignin can be purified and/or activated if needed for thefurther processing.

In one embodiment of the present invention the lignin is separated frompure biomass. The separation process can begin with liquidizing thebiomass with strong alkali or strong acid followed by a neutralizationprocess. After the alkali treatment the lignin can be precipitated in asimilar manner as presented above. In one embodiment of the presentinvention the separation of lignin from biomass comprises a step ofenzyme treatment. The enzyme treatment modifies the lignin to beextracted from biomass. Lignin separated from pure biomass issulphur-free and thus valuable in further processing.

In one embodiment of the present invention the lignin is steam explosionlignin. Steam explosion is a pulping and extraction technique that canbe applied to wood and other fibrous organic material.

By “biorefinery lignin” is to be understood in this specification,unless otherwise stated, lignin that can be recovered from a refiningfacility or process where biomass is converted into fuel, chemicals andother materials.

By “supercritical separation lignin” is to be understood in thisspecification, unless otherwise stated, lignin that can be recoveredfrom biomass using supercritical fluid separation or extractiontechnique. Supercritical conditions correspond to the temperature andpressure above the critical point for a given substance. Insupercritical conditions, distinct liquid and gas phases do not exist.Supercritical water or liquid extraction is a method of decomposing andconverting biomass into cellulosic sugar by employing water or liquidunder supercritical conditions. The water or liquid, acting as asolvent, extracts sugars from cellulose plant matter and lignin remainsas a solid particle.

In one embodiment of the present invention the lignin is hydrolysislignin. Hydrolysed lignin can be recovered from paper-pulp orwood-chemical processes.

In one embodiment of the present invention the lignin originates from anorganosols process. Organosolv is a pulping technique that uses anorganic solvent to solubilize lignin and hemicellulose.

In one embodiment of the present invention the temperature of thecomposition is kept, in step a), preferably at 15-55° C., morepreferably at 20-50° C., and even more preferably at 30-45° C. Keepingthe temperature of the composition in step a) at 0-60° C., andpreferably at the above mentioned ranges, allows the lignin to dissolveinto the aqueous composition, which contains a compound selected fromthe class of phenols, while, at least for most part of the lignin,hindering it from reacting with the compound selected from the class ofphenols.

The pH value of the composition in step a) and in step b) can beselected depending on the final application of the binder composition tobe produced.

In one embodiment of the present invention, the pH of the composition iskept, in step a), at the pH value of 4-10, preferably at the pH value of4.5-9.5, more preferably at the pH value of 5-9, and even morepreferably at the pH value of 5.5-8.5. In one embodiment of the presentinvention the pH of the composition is kept, in step b), preferably atthe pH value of 6-10, more preferably at the pH value of 6.5-9.5, andeven more preferably at the pH value of 7-9. These kinds of pH rangesmay be used in step a) and in step b) when producing a bindercomposition for high-pressure laminates.

In one embodiment of the present invention, the pH of the composition iskept, in step a), at the pH value of 4-14, preferably at the pH value of7-13.5, and more preferably at the pH value of 8.5-13. In one embodimentof the present invention the pH of the composition is kept, in step b),preferably at the pH value of 7-14, more preferably at the pH value of9-13.5, and even more preferably at the pH value of 10-13. These kindsof pH ranges may be used in step a) and in step b) when producing abinder composition for plywood.

The composition is treated, in step b), at a temperature of 60-100° C.In one embodiment of the present invention, the composition is heated,in step b), preferably at a temperature of 70-95° C., and morepreferably at a temperature of 75-90° C.

In one embodiment of the present invention step b) is carried out for 10minutes-2 hours, preferably for 1 hour-1.5 hours.

In one embodiment of the present invention the alkali is sodiumhydroxide, potassium hydroxide, or a combination thereof.

In one embodiment of the present invention the concentration of alkaliis 0.1-11 weight-%, and preferably 0.5-9 weight-% based on the totalweight of the composition in step b). In one embodiment of the presentinvention the concentration of alkali is 0.1-5 weight-%, and preferably0.5-2 weight-% based on the total weight of the composition in step b).In one embodiment of the present invention the concentration of alkaliis 3-15weight-%, preferably 5-12, and more preferably 6-10 weight-%based on the total weight of the composition in step b).

In one embodiment of the present invention the concentration of ligninin step a) is 10-40 weight-%, and preferably 20-30 weight-% based on thetotal weight of the composition in step a).

In one embodiment of the present invention the concentration of thecompound selected from the class of phenols in step a) is 10-50weight-%, preferably 20-50 weight-%, and more preferably 20-45 weight-%based on the total weight of the composition in step a).

The step of heating the formed composition in step c) is carried out forpolymerizing the reactant components, i.e. lignin, the compound selectedfrom the class of phenols, and the crosslinking agent, such that theviscosity of the binder composition is increased. The heating can becontinued until a predetermined viscosity value is formed. Thepredetermined viscosity value of the final binder composition may varydepending on the specific application where the binder composition is tobe used.

In one embodiment of the present invention the predetermined viscosityvalue of the final binder composition is at least 40 cP, preferably atleast 50 cP, and more preferably at least 80 cP. In one embodiment ofthe present invention the predetermined viscosity value of the finalbinder composition is at least 40 but not more than 250 cP, preferablyat least 50 cP but not more than 150 cP, and more preferably at least 80but not more than 120 cP.

In one embodiment of the present invention the predetermined viscosityvalue of the final binder composition is at least 250 cP, preferably atleast 300 cP, and more preferably at least 500 cP. In one embodiment ofthe present invention the predetermined viscosity value of the finalbinder composition is at least 250 cP but not more than 1500 cP,preferably at least 300 cP but not more than 1200 cP, and morepreferably at least 500 but not more than 1000 cP.

The viscosity is measured at 25° C. using a rotary viscometer.

In one embodiment of the present invention, step c) comprises heatingthe composition preferably at a temperature of 65-95° C., morepreferably at a temperature of 70-90, and even more preferably at atemperature of 75-85° C.

In one embodiment of the present invention the crosslinking agent isselected from a group consisting of an aldehyde, a derivative of analdehyde, an aldehyde forming compound and combinations thereof. In oneembodiment of the present invention the derivative of an aldehyde ishexamethylenetetramine, paraformaldehyde or trioxane. In one embodimentof the present invention the crosslinking agent is selected from a groupconsisting of an aromatic aldehyde, glyoxal, furfuryl alcohol,caprolactam and glycol compounds. The aldehyde can be formaldehyde. Thearomatic aldehyde can be furfuryl aldehyde. In one embodiment of thepresent invention the crosslinking agent is an aldehyde, and preferablyformaldehyde, paraformaldehyde or a combination thereof.

In one embodiment of the present invention step c) is carried out in thepresence of a catalyst. In one embodiment of the present invention thecatalyst is selected from a group consisting of sodium hydroxide,potassium hydroxide and any mixture thereof.

In one embodiment of the present invention the pH of the composition iskept, in step c), preferably at the pH value of 6-10, more preferably atthe pH value of 6.5-9.5, and even more preferably at the pH value of7-9.

In one embodiment of the present invention the pH of the composition iskept, in step c), preferably at the pH value of 7-14, more preferably atthe pH value of 9-13.5, and even more preferably at the pH value of10-13.

The present invention further relates to the use of lignin treated bythe method according to the present invention for the production of abinder composition.

The present invention further relates to a binder composition obtainableby the method according to the present invention.

The present invention further relates to an adhesive compositioncomprising the binder composition according to the present invention.The adhesive composition can further comprise one or more adhesivecomponents selected from a group consisting of other binders, extenders,additives, catalysts and fillers.

The present invention further relates to the use of a binder compositionobtainable by the method according to the present invention, wherein thepH of the composition is kept in step a) at a value of 4-10 and in stepb) at a value of 6-10, for producing a laminate, and preferably ahigh-pressure laminate.

The present invention further relates to the use of a binder compositionobtainable by the method according to the present invention, wherein thepH of the composition is kept in step c) at a value of 6-10 forproducing a laminate, and preferably a high-pressure laminate.

The present invention further relates to the use of a binder compositionobtainable by the method according to the present invention, wherein thepH of the composition is kept in step a) at a value of 4-10 and in stepb) at a value of 6-10, for producing a foundry material, a protectivecoating, a friction material, an abrasive material, glass wool, rockwool, a prepreg, a shuttering film, an overlay, a molding component or afiber reinforced composite.

The present invention further relates to the use of a binder compositionobtainable by the method according to the present invention, wherein thepH of the composition is kept in step c) at a value of 6-10, forproducing a foundry material, a protective coating, a friction material,an abrasive material, glass wool, rock wool, a prepreg, a shutteringfilm, an overlay, a molding component or a fiber reinforced composite.

The present invention further relates to the use of a binder compositionobtainable by the method according to the present invention, wherein thepH of the composition is kept in step a) at a value of 4-14 and in stepb) at a value of 7-14, for producing a particle board, an orientedstrand board, a chip board, an intrallam, a gluelam, a hardboard, awaferboard, a fiber board, a, plywood, or a wood adhesive.

The present invention further relates to the use of a binder compositionobtainable by the method according to the present invention, wherein thepH of the composition is kept, in step c), preferably at the pH value of7-14, for producing a particle board, an oriented strand board, a chipboard, an intrallam, a gluelam, a hardboard, a waferboard, a fiberboard, a, plywood, or a wood adhesive.

The embodiments of the invention described hereinbefore may be used inany combination with each other. Several of the embodiments may becombined together to form a further embodiment of the invention. Amethod, a composition or a use, to which the invention is related, maycomprise at least one of the embodiments of the invention describedhereinbefore.

An advantage of the method according to the present invention is that itis possible to treat lignin in a manner that enables the production of alow pH binder composition, i.e. a binder composition with a neutral oracidic pH range. The lignin treated with the method according to thepresent invention has an open structure making it more reactive wherebythe production of low pH binder composition is possible with lignin.

An advantage of the present invention is that a bio-based bindercomposition suitable to be used for the production of high-pressurelaminates can be produced by the method according to the presentinvention. An advantage of the present invention is that a moreenvironmentally friendly binder composition can be produced forhigh-pressure laminates.

EXAMPLES

Reference will now be made in detail to the embodiments of the presentinvention, an example of which is illustrated in the accompanyingdrawing.

The description below discloses some embodiments of the invention insuch a detail that a person skilled in the art is able to utilize theinvention based on the disclosure. Not all steps of the embodiments arediscussed in detail, as many of the steps will be obvious for the personskilled in the art based on this specification.

FIG. 1 illustrates a method according to one embodiment of the presentinvention for treating lignin.

Before the treatment of lignin is started, the source of lignin ischosen. Also the other components and their amounts to be used in themethod according to the present invention are selected. If needed, thecomponents used in the method of FIG. 1 can be pre-treated to besuitable for the lignin treatment processes.

Following the various preparations and pretreatments, in one of theembodiments of the present invention shown in FIG. 1, step a) is carriedout. Step a) comprises dissolving lignin into an aqueous compositioncontaining a compound selected from the class of phenols. Thetemperature of the composition is kept at 0-60° C.

After the step of dissolving lignin, the composition formed in step a)is allowed to react while keeping the temperature of the composition at60-100° C. and the pH of the composition at a pH value of 6-14.

In one embodiment of the present invention, after the step of dissolvinglignin, the composition formed in step a) is subjected to an alkalitreatment for alkalating the lignin in step b). The alkali can be addedto the composition in step a) and/or in step b). The alkali is ahydroxide of an alkali metal.

Step a) and step b) result in the lignin being suitable for furtherproduction steps and being suitable for being covalently bonded withe.g. formaldehyde.

FIG. 2 illustrates a method according to one embodiment of the presentinvention for producing a binder composition.

The method illustrated in FIG. 2 begins with treating lignin in step a)and step b) in accordance with the method described above for FIG. 1.

After step b) the composition formed in step b) is mixed with acrosslinking agent in step c). The formed composition is heated at atemperature of 60-100° C. for allowing the reactant components, i.e. thelignin, the compound selected from the class of phenols and thecrosslinking agent, in the composition to react with each other forforming a binder composition. The pH of the composition is kept in stepc) at a pH value of 6-14. The heating of the composition is continueduntil a desired, predetermined, viscosity value of the bindercomposition is reached.

As a result of step c) a binder composition having desired propertiesand especially having high ratio of bio-based components is produced.This binder composition can be used as such for gluing applications orit can be further processed with other adhesive components for producingan adhesive composition.

EXAMPLE 1 Activating Lignin and the Use of Activated Lignin for theProduction of a Binder Composition

In this example lignin was firstly treated with phenol and sodiumhydroxide. The following components and their amounts were used:

Material MW Concentration Mass, g NaOH 40 50% 43.3 Water 18  0% 529.0Lignin 180 70% 509.0 Phenol 94 90% 594.0

Firstly a composition of water and phenol was formed. Then lignin wasslowly added to the composition with agitation while keeping thetemperature of the composition below 30° C. and the pH of thecomposition below a value of 8. When all of the lignin had been added,sodium hydroxide was added to the composition while heating thecomposition up to a temperature of 90° C. The pH of the composition waskept at a value of below 9. The heating of the composition was continuedfor 10 minutes at the temperature of 90° C.

Lignin treated as above described was thereafter used for producing abinder composition. 438 g of paraformaldehyde was added to the aboveformed composition in a stepwise manner. Thereafter the pH of thecomposition was measured to have a value of 7.70. The formed compositionwas heated at a temperature of about 80° C. and the heating wascontinued for 2 hours and 15 minutes, during which time the viscosityincreased to 130 cP as measured at 25° C. using a rotary viscometer.

The formed binder composition was thereafter analyzed. The results ofthe analysis can be seen in Table 1.

TABLE 1 Analysis results Specifications MR 1.9 Solids (2 g, 2 h at 120°C.), % 54.7 Viscosity, cP 125 pH 8.05 WT >1/9 Gel time 100° C., min 61

In Table 1 MR stands for molecular ratio, i.e. the ratio ofmol(paraformaldehyde)/mol(phenol+lignin). In Table 1 WT stands for watertolerance, i.e. describes how much water can be added to resin beforeresin starts to precipitate.

The gel time was determined by adding 0.5 ml of the sample in a testtube with a rod. The sample was not to be stirred. The test tube washeated to 100° C. in a glycerin or oil bath without mixing. The timeuntil the sample became pasty (melted solid) was measured after whichthe measurement was completed.

From the results indicated in Table 1 it can be seen that the solidscontent is on a suitable level for the binder composition to be used forhigh-pressure laminates. The water tolerance is better than fortraditionally used phenol-formaldehyde binder compositions used forlaminates.

EXAMPLE 2 Activating Lignin and the Use of Activated Lignin for theProduction of a Binder Composition

In this example lignin was firstly treated with phenol and sodiumhydroxide. The following components and their amounts were used:

Material MW Concentration Mass, g NaOH 40 50% 48.0 Water 18  0% 537.0Lignin 180 70% 650.0 Phenol 94 90% 506.0

Firstly a composition of water and phenol was formed. Then lignin wasslowly added to the composition with agitation while keeping thetemperature of the composition below 30° C. and the pH of thecomposition below a value of 5. When all of the lignin had been added,sodium hydroxide was added to the composition while heating thecomposition up to a temperature of 90° C. The pH of the composition waskept at a value of below 9. The heating of the composition was continuedfor 10 minutes at the temperature of 90° C.

Lignin treated as above described was thereafter used for producing abinder composition. 421 g of paraformaldehyde was added to the aboveformed composition in a stepwise manner. Thereafter the pH was measuredto have a value of 7.70. The formed composition was heated at atemperature of about 78° C. and the heating was continued for 1 hoursand 23 minutes, during which time the viscosity increased to 130 cP asmeasured at 25° C. using a rotary viscometer.

The formed binder composition was thereafter analyzed. The results ofthe analysis can be seen in Table 2.

TABLE 2 Analysis results Specifications MR 1.9 Solids (2 g, 2 h at 120°C.), % 52.38 Viscosity, cP 115 pH 7.85 WT >1/9 Gel time 100° C., min 88

In Table 2 MR stands for molecular ratio, i.e. the ratio ofmol(paraformaldehyde)/mol(phenol+lignin). In Table 2 WT stands for watertolerance, i.e. describes how much water can be added to resin beforeresin starts to precipitate.

The gel time was determined as above described for example 1.

From the results indicated in Table 2 it can be seen that the solidscontent is on a suitable level for the binder composition to be used forhigh-pressure laminates. The water tolerance is better than fortraditionally used phenol-formaldehyde binder compositions used forlaminates.

EXAMPLE 3 Producing High-Pressure Laminate

High-pressure laminate was produced by fusing together under heating andpressure several layers of Kraft paper impregnated with the bindercomposition as produced in Example 1. The formed laminates werethereafter tested for boiling water and heat tolerance. The tests wereperformed according to standard SFS-EN 438-2 (high-pressure decorativelaminates (HPL)). The samples were evaluated for delamination andblisters. Both tests were based on the evaluation of a visual appearanceafter immersion for 2 hours in boiling water and after heating for 30minutes in oven at 150° C. The binder compositions in which 40 and 50%of phenol was replaced with lignin, the heat and boiling water and heattolerances were good and no blisters were observed.

EXAMPLE 4 Activating Lignin and the Use of Activated Lignin for theProduction of a Binder Composition

In this example lignin was firstly treated with phenol and sodiumhydroxide. The following components and their amounts were used:

Material MW Concentration Mass, g NaOH 40 50% 266 Water 18  0% 500Lignin 180 68.5%  602 Phenol 94 90% 458

Firstly lignin was mixed with water and then sodium hydroxide was addedto the formed composition. The pH was increased to a value of about13.8. To this composition, the phenol was added. The temperature of thecomposition was kept under 45° C. while dissolving lignin into thecomposition.

Then the temperature was increased to about 75° C. and the heating wascontinued for about 1 h. The pH of the composition was kept at a valueof 10-11 during the heating of the composition.

Lignin treated as above described was thereafter used for producing abinder composition. 490 g of paraformaldehyde was added to the aboveformed composition in a stepwise manner. The formed composition washeated at a temperature of about 83-85° C. and until the viscosityincreased to 315 cP as measured at 25° C. using a rotary viscometer.

The formed binder composition was thereafter analyzed. The results ofthe analysis can be seen in Table 3.

TABLE 3 Analysis results Specifications MR 1.9 Solids (2 g, 2 h at 120°C.), % 42.3 Viscosity, cP 315 pH 12.1 Gel time 100° C., min 48

In Table 3 MR stands for molecular ratio, i.e. the ratio ofmol(paraformaldehyde)/mol(phenol+lignin).

The gel time was determined as above described for example 1.

From the results indicated in Table 3 it can be seen that the propertiesof the formed binder composition are suitable for wood adhesives and tobe used e.g. in plywood and oriented strand boards.

EXAMPLE 5 Activating Lignin and the Use of Activated Lignin for theProduction of a Binder Composition

In this example lignin was firstly treated with phenol. The followingcomponents and their amounts were used:

Material MW Concentration Mass, g Water 18  0% 584.6 Lignin 180 70%708.0 Phenol 94 90% 551.0

Firstly a composition of water and phenol was formed. Then lignin wasslowly added to the composition with agitation while keeping thetemperature of the composition below 40° C. and the pH of thecomposition below a value of 6. When all of the lignin had been added,the composition was heated up to a temperature of 90° C. The pH of thecomposition was kept at a value of about 7.

Lignin treated as above described was thereafter used for producing abinder composition. 458.4 g of paraformaldehyde was added to the aboveformed composition in a stepwise manner. Also catalyst, i.e. 52.3 g ofsodium hydroxide, was added to the composition in a stepwise manner. ThepH of the composition was kept at a value of 7-8. The formed compositionwas heated at a temperature of 80-90° C. The heating was of thecomposition was carried out for a total of about 1 hour.

The formed binder composition was thereafter analyzed. The results ofthe analysis can be seen in Table 4.

TABLE 4 Analysis results Specifications MR 1.9 Solids (2 g, 2 h at 120°C.), % 52.1 Viscosity, cP 135 pH 7.31 WT >1/10 Gel time 100° C., min 85

In Table 4 MR stands for molecular ratio, i.e. the ratio ofmol(paraformaldehyde)/mol(phenol+lignin). In Table 4 WT stands for watertolerance, i.e. describes how much water can be added to resin beforeresin starts to precipitate.

The gel time was determined as above described for example 1.

From the results indicated in Table 4 it can be seen that the solidscontent is on a suitable level for the binder composition to be used inimpregnation applications such as laminates and shuttering films. Thewater tolerance is better than for traditionally usedphenol-formaldehyde binder compositions used for laminates.

EXAMPLE 6 Treating Lignin and the Use of Activated Lignin for theProduction of a Binder Composition

In this example lignin was firstly treated with phenol and sodiumhydroxide. The following components and their amounts were used:

Material MW Concentration Mass, g NaOH 40 50% 66.0 Water 18  0% 250.0Lignin 180 70% 879.0 Phenol 94 90% 684.0

Firstly a composition of water and phenol was formed. Then lignin wasslowly added to the composition with agitation while keeping thetemperature of the composition at about 40° C. and the pH of thecomposition below a value of 5.5.

When all of the lignin had been added, sodium hydroxide was added to thecomposition while keeping the temperature of the composition at about70-75° C. The pH of the composition was kept at a value of below 8.5.Heating of the composition was then continued for 10 minutes at thetemperature of 90° C.

Lignin treated as above described was thereafter used for producing abinder composition. 568 g of paraformaldehyde was added to the aboveformed composition in a stepwise manner. Thereafter the pH of thecomposition was measured to have a value of about 8. The formedcomposition was heated at a temperature of about 76° C. and the heatingwas continued for 1 hour and 45 minutes, during which time the viscosityincreased to 930 cP as measured at 25° C. using a rotary viscometer.

The formed binder composition was thereafter analyzed. The results ofthe analysis can be seen in Table 5.

TABLE 5 Analysis results Specifications MR 1.9 Solids (2 g, 2 h at 120°C.), % 65.1 Viscosity, cP 780 pH 7.62 WT >1/10 Gel time 130° C., min 8

In Table 5 MR stands for molecular ratio, i.e. the ratio ofmol(paraformaldehyde)/mol(phenol+lignin). In Table 5 WT stands for watertolerance, i.e. describes how much water can be added to resin beforeresin starts to precipitate.

The gel time was determined as above described for example 1 but using atemperature of 130° C.

The binder composition formed was used for preparing a pre-preg byadding about 2 weight-%, based on the weight of the binder composition,of diethylene glycol (DEG) and then below 1 weight-%, based on theweight of binder composition, of glycolic acid to the cooled bindercomposition.

EXAMPLE 7 Formation of Rock Wool

In this example lignin was firstly treated with phenol and sodiumhydroxide. The following components and their amounts were used:

Material MW Concentration Mass, g NaOH 40 50% 111.7 Water 18  0% 227.2Lignin 180 70% 171.9 Phenol 94 90% 534.5

Firstly lignin was added to a composition of water and phenol. To thiscomposition 45.4 g of borax was added in a stepwise manner. Borax is acommonly used product in rock wool to enhance fire resistance and to actas an anti-moulding agent. Borax does not take part in the reactionswhere lignin is dissolved and allowed to react with phenol and NaOH.Borax can be added to the composition in the beginning of the process toensure even distribution in the polymer matrix but it could also beadded only after the binder composition formation. After the borax hadbeen added, sodium hydroxide was added to the composition. Thetemperature of the composition was about 20-42° C. when dissolvinglignin into this composition.

Thereafter the temperature was increased to about 65° C. for allowinglignin to react with phenol and sodium hydroxide for about 1 hour whilekeeping the pH of the composition at about 10.

After the lignin had been activated by the above procedure, 1093.5 g offormaldehyde was added to the composition and the composition was heatedat a temperature of 65° C. for about 2.5 hours. The pH was kept at about8.8. Then the composition was cooled to a temperature of 40° C., andabout 1 weight-%, based on the weight of the composition, of boric acidwas added followed by adding about 4-5 weight-%, based on the weight ofthe composition, of urea.

It is obvious to a person skilled in the art that with the advancementof technology, the basic idea of the invention may be implemented invarious ways. The invention and its embodiments are thus not limited tothe examples described above; instead they may vary within the scope ofthe claims.

1. A method for treating lignin, characterized in that the methodcomprises the following steps: a) dissolving lignin into an aqueouscomposition, which contains a compound selected from the class ofphenols, while keeping the temperature of the composition at 0-60° C.;and b) allowing the composition to react while keeping the temperatureof the composition at 60-100° C. and the pH of the composition at a pHvalue of 6-14.
 2. The method of claim 1, wherein the compound selectedfrom the class of phenols is selected from a group consisting of phenol,cresol, resorcinol and combinations thereof.
 3. The method of claim 1,wherein step b) comprises allowing the composition to react with alkali,wherein the alkali comprises a hydroxide of an alkali metal.
 4. Themethod of claim 1, wherein the temperature of the composition is kept,in step a), at 15-55° C.
 5. The method of claim 1, wherein the pH of thecomposition is kept, in step a), at the pH value of 4-10.
 6. The methodof claim 5, wherein the pH of the composition is kept, in step b), atthe pH value of 6-10.
 7. The method of claim 1, wherein the pH of thecomposition is kept, in step a), at the pH value of 4-14.
 8. The methodof claim 7, wherein the pH of the composition is kept, in step b), atthe pH value of 7-14.
 9. The method of claim 1, wherein the compositionis heated, in step b), at a temperature of 70-95° C.
 10. A method forproducing a binder composition, characterized in that the methodcomprises the following steps: a) dissolving lignin into an aqueouscomposition, which contains a compound selected from the class ofphenols, while keeping the temperature of the composition at 0-60° C.;b) allowing the composition to react while keeping the temperature ofthe composition at 60-100° C. and the pH of the composition at a pHvalue of 6-14; and c) mixing the composition formed in step b) with acrosslinking agent and heating the composition at a temperature of60-100° C. while keeping the pH of the composition at a pH value of6-14.
 11. The method of claim 10, wherein step c) comprises heating thecomposition at a temperature of 65-95° C.
 12. The method of claim 10,wherein the pH of the composition is kept, in step a), at the pH valueof 4-10.
 13. The method of claim 12, wherein the pH of the compositionis kept, in step b), at the pH value of 6-10.
 14. The method of claim10, wherein the pH of the composition is kept, in step a), at the pHvalue of 4-14.
 15. The method of claim 14, wherein the pH of thecomposition is kept, in step b), at the pH value of 7-14.
 16. The methodof claim 10, wherein the pH of the composition is kept, in step c), atthe pH value of 6-10.
 17. The method of claim 10, wherein the pH of thecomposition is kept, in step c), at the pH value of 7-14.
 18. The methodof claim 10, wherein the crosslinking agent is selected from the groupconsisting of an aldehyde, formaldehyde, paraformaldehyde or acombination thereof.
 19. (canceled)
 20. A binder composition obtainableby the method of claim
 10. 21. An adhesive composition comprising thebinder composition of claim
 20. 22-24 (canceled)